The present invention relates to a composition for the treatment of textiles, in particular to a fabric care composition containing a UV absorber, and to a method of treating textiles with the composition, which method imparts to textile fibre material so treated, in addition to an excellent sun protection factor (SPF) value, and other desirable properties.
It is known that light radiation of wavelengths 280-400 nm permits tanning of the epidermis. Also known is that rays of wavelengths 280-320 nm (termed UV-B radiation), cause erythemas and skin burning which can inhibit skin tanning.
Radiation of wavelengths 320-400 nm (termed UV-A radiation) is known to induce skin tanning but can also cause skin damage, especially to sensitive skin which is exposed to sunlight for long periods. Examples of such damage include loss of skin elasticity and the appearance of wrinkles, promotion of the onset of erythemal reaction and the inducement of phototoxic or photoallergic reactions.
Any effective protection of the skin from the damaging effects of undue exposure to sunlight clearly needs to include means for absorbing both UV-A and UV-B components of sunlight before they reach the skin surface.
Traditionally, protection of exposed human skin against potential damage by the UV components in sunlight has been effected by directly applying to the skin a preparation containing a UVA. In areas of the world, e.g. Australia and America, which enjoy especially sunny climates, there has been a great increase in the awareness of the potential hazards of undue exposure to sunlight, compounded by fears of the consequences of alleged damage to the ozone layer. Some of the more distressing embodiments of skin damage caused by excessive, unprotected exposure to sunlight are development of melanomas or carcinomas on the skin.
One aspect of the desire to increase the level of skin protection against sunlight has been the consideration of additional measures, over and above the direct protection of the skin.
For example, consideration has been given to the provision of protection to skin covered by clothing and thus not directly exposed to sunlight.
Most natural and synthetic textile materials are at least partially permeable to UV components of sunlight. Accordingly, the mere wearing of clothing does not necessarily provide skin beneath the clothing with adequate protection against damage by UV radiation. Although clothing containing a deeply coloured dye and/or having a tight weave texture may provide, a reasonable level of protection to skin beneath it, such clothing is not practical in hot sunny climates, from the standpoint of the personal comfort of the wearer.
There is a need, therefore, to provide protection against UV radiation for skin which lies underneath clothing, including lightweight summer clothing, which is undyed or dyed only in pale shades. Depending on the nature of the dyestuff, even skin beneath clothing dyed in some dark shades may also require protection from UV radiation.
Such lightweight summer clothing normally has a density of of less than 200 g/m2 and has a sun protection factor rating between 1.5 and 20, depending on the type of fibre from which the clothing is manufactured.
The SPF rating of a sun protectant (sun cream or clothing) may be defined as the multiple of the time taken :or the average person wearing the sun protectant to suffer sun burning under average exposure to sun. For example, if an average person would normally suffer sun bum after 30 minutes under standard exposure conditions, a sun protectant having an SPF rating of 5 would extend the period of protection from 30 minutes to 2 hours and 30 minutes. For people living in especially sunny climates, where mean sun burn times are minimal, e.g. only 15 minutes for an average fair-skinned person at the hottest time of the day, SPF ratings of about 20 are desired for lightweight clothing.
The selection of a suitable UVA, for use in a method for effecting an increase in the SPF value of a textile fibre material (often referred to as a xe2x80x9cU cuttingxe2x80x9d treatment method), has to take into account the fact that the treated textile fibre material must satisfy performance criteria in a wide range of areas, such as washfastness, lightfastness and tear resistance, apart from its SPF value.
For example, the currently known non-reactive UVAs generally exhibit an inadequate washfastness when applied to cotton. Consequently, their use in UV cutting applications (and also for the purpose of improving the lightfastness) is limited.
It is already known from WO 86/2392, that a fabric softening composition may comprise:
a) 20-89.9% by weight of a specified alkoxylated xcex2-sitosterol;
b) 10-79.9% by weight of di(C12-C22-alkyl)dimethylammonium chloride or a specified imidazoline derivative;
c) 0.01-10% by weight of a UV-absorber; and
d) 0-10% by weight of one or more additives. The specified alkoxylated xcex2-sitosterol components of these known compositions appear to be rather inaccessible compounds which are not commercially available. Moreover, the specific UV-absorbers described in WO 86/2392, with the exception of 2-hydroxy-4-cyanobenzophenone are, in fact, fluorescent whitening agents rather than UV-absorbers.
Surprisingly, it has now been found that by applying, to a washed article of clothing, a rinse cycle fabric care formulation comprising a specific UV absorber, especially a rinse cycle fabric softener comprising a specific UV absorber, the SPF factor of clothing so treated can be significantly increased, without the need to include an alkoxylated xcex2-sitosterol in the rinse cycle fabric care formulation.
The present invention provides, therefore, as a first aspect, a stable, concentrated fabric rinse composition comprising:
a) 0.1 to 20, preferably 1 to 10% by weight of a UV absorber selected from a hydroxyaryl-1,3,5triazine, a sulphonated-1,3,5-triazine, an o-hydroxyphenylbenzotriazole or a 2-aryl-2H-benzotriazole, based on the total weight of the composition;
b) a fabric care ingredient, preferably a fabric softener, a stain release or stain repellant ingredient of a waeter-proofing agent; and
c) the remainder being substantially water.
The fabric care ingredient is preferably present in an amount of from 5 to 25, preferably 10 to 20% by weight, based on the total weight of the composition.
The present invention provides, as a second aspect, a stable, concentrated rinse cycle fabric softener composition comprising:
a) 0.1 to 20, preferably 1 to 10% by weight of a UV absorber selected from a hydroxyaryl-1,3,5-triazine, a sulphonated-1,3,5-triazine, an o-hydroxyphenylbenzotriazole or a 2-aryl-2H-benzotriazole, based on the total weight of the composition;
b) 5 to 25, preferably 10 to 20% by weight of a cationic fabric softening agent based on the total weight of the composition; and c) the remainder being substantially water.
Preferred examples of cationic fabric softening agents include imidazolines and quaternary ammonium compounds as well as mixtures thereof.
Preferred imidazoline cationic fabric softening agents are those having the formula: 
in which R is hydrogen or C1-C4alkyl; R1 is a C8-C30aliphatic residue; R2 is hydrogen, a C8-C30aliphatic residue, C1-C4alkyl, C1-C4halogenoalkyl, C1-C4hydroxyalkyl or a group xe2x80x94C2H4xe2x80x94OC(xe2x95x90O)xe2x80x94R5 or xe2x80x94C2H4xe2x80x94N(R4)xe2x80x94C(xe2x95x90O)xe2x80x94R5 in which R4 is hydrogen or C8-C10alkyl an R5 is hydrogen or C1-C4alkyl; R3 is a C8-C30aliphatic residue, C1-C4alkyl, C1-C4halogenoalkyl, C1-C4hydroxyalkyl or a group xe2x80x94C2H4xe2x80x94OC(xe2x95x90O)xe2x80x94R5 or xe2x80x94C2H4xe2x80x94N(R4)xe2x80x94C(xe2x95x90O)xe2x80x94R5 in which R4 and R5 have their previous significance; and X is an anion.
Preferably R is hydrogen or methyl; R1 is C14-C18alkyl or C14-C18alkenyl; R2 is hydrogen, C14-C18alkyl, C14-C18alkenyl, C1-C4alkyl, C1-C4halogenoalkyl or C1-C4hydroxyalkyl; and R3 is a group xe2x80x94C2H4xe2x80x94OC(xe2x95x90O)xe2x80x94R5 or xe2x80x94C2H4xe2x80x94N(R4)xe2x80x94C(xe2x95x90O)xe2x80x94R5 in which R4 is hydrogen or C8-C30alkyl and R5 is hydrogen or C1-C4alkyl.
Preferred anions X include chloride, bromide, iodide, fluoride, sulfate, methosulfate, nitrite, nitrate or phosphate anions, as well as carboxylate anions such as acetate, adipate, phthalate, benzoate, stearate or oleate anions.
Specific examples of preferred compounds of formula (1) include:
2-tallow-1-(2-stearoyloxyethyl)-imidazoline chloride,
2-tallow-1-(2-stearoyloxyethyl)-imidazoline sulfate,
2-tallow-1-(2-stearoyloxyethyl)-imidazoline methosulfate,
2-tallow-1-methyl-3-(2-stearoylamidoethyl)-imidazoline chloride,
2-tallow-1-methyl-3-(2-stearoylamidoethyl)-imidazoline sulfate,
2-tallow-1-methyl-3-(2-stearoylamidoethyl)-imidazoline methosulfate,
2-heptadecyl-1-methyl-1-oleylamidoethyl-imidazolinium-metho-sulfate,
2-heptadecyl-1-methyl-1-(2-stearoylamido)ethyl-imidazolinium-sulfate,
2-heptadecyl-1-methyl-1-(2-stearoylamido)ethyl-imidazolinium-chloride
2-coco-1-(2-hydroxyethyl)-1-benzyl-imidazolinium-chloride
2-coco-1-(2-hydroxyethyl)-1-(4-chlorobutyl)-imidazolinium-chloride
2-coco-1-(2-hydroxyethyl)-1-octadecenyl-imidazolinium-chloride
2-tallow-1-(2-hydroxyethyl)-1-benzyl-imidazolinium-chloride
2-tallow-1-(2-hydroxyethyl)-1-(4-chlorobutyl)-imidazolinium-chloride
2-heptadecenyl-1-(2-hydroxyethyl)1-(4-chlorobutyl)-imidazolinium-chloride
2-heptadecenyl-1-(2-hydroxyethyl)-1-benzyl-imidazolinium-chloride and
2-heptadecenyl-1-(2-hydroxyethyl)-1-octadecyl-imidazolinium-chloride
One class of preferred quaternary ammonium compounds is that having the formula: 
in which R6 is a C8-C30aliphatic residue, R7, R8, R9, R10 and R11, independently, are hydrogen, C1-C4alkyl or C1-C4hydroxyalkyl, X has its previous significance, m is an integer from 1 to 5 and n is an integer from 2 to 6.
Preferred compounds of formula (2) are those in which R6 is C12-C18alkyl and R7, R8, R9, R10 and R11, independently, are C1-C4alkyl, especially methyl.
Specific examples of preferred compounds of formula (2) are:
N-(tallow)-N,N,Nxe2x80x2,Nxe2x80x2-tetramethyl-1,3-propanediammoniumdimethosulfate
N-(tallow)-N,Nxe2x80x2,Nxe2x80x2-trimethyl-1,3-propanediammoniumdimethosulfate
N-(tallow)-N,N,Nxe2x80x2,Nxe2x80x2,Nxe2x80x2-pentamethyl-1,3-propanediammoniumdimethosulfate
N-oleyl-N,N,Nxe2x80x2,Nxe2x80x2,Nxe2x80x2-pentamethyl-1,3-propanediammoniumdimethosulfate
N-stearyl-N,N,Nxe2x80x2,Nxe2x80x2,Nxe2x80x2-pentamethyl-1,3-propanediammoniumdimethosulfate and
N-stearyloxypropyl-N,Nxe2x80x2,Nxe2x80x2-tris(3-hydroxypropyl)-1,3-propanediammoniumdiacetate.
A further class of preferred quaternary ammonium compounds is that having the formula: 
in which X has its previous significance and the groups R12 may be the same or different and each is a C1-C30aliphatic residue, provided that at least one group R12, and preferably two groups R12 are C14-C30alkyl. Preferably, the remaining groups R12 are C1-C4alkyl, especially methyl or ethyl.
Specific preferred compounds of formula (3) are:
distearyldimethylammonium chloride
dilauryldimethylammonium chloride
dihexadecyldimethylammonium chloride
distearyldimethylammonium bromide
distearyldimethylammonium methosulfate and
distearyldi-(isopropyl)-ammonium chloride.
The UV absorber used readily absorbs UV light, especially in the range xcex=300 to 400 nm, and converts the absorbed energy, by a chemical intermediate reaction, into non-interfering, stable compounds or into non-interfering forms of energy. The UV absorber used should, of course, be compatible with the rinse cycle fabric softener composition. Preferably, the UV absorber used is one which is capable of being absorbed on to the washed textile article during a rinse cycle fabric softener treatment.
Such known UV absorbers for use in the present invention are described, for example, in the U.S. Pat. Nos. 3,118,887, 3,259,627, 3,293,247, 3,382,183, 3,423,360, 4,127,586, 4,141,903, 4,230,867, 4,675,352 and 4,698,064.
One preferred class of triazine UV absorbers is that having the formula: 
in which R13 and R14, independently, are hydrogen, hydroxy or C1-C5alkoxy.
A second preferred class of triazine UV absorbers is that having the formula: 
in which at least one of R15, R16 and R17 is a radical of formula: 
in which M is hydrogen, sodium, potassium, calcium, magnesium, ammonium, mono-, di-, tri- or tetra-C1-C4alkylammonium, mono-, di- or tri-C1-C4hydroxyalkylammonium or ammonium that is di- or tri-substituted by a mixture of C1-C4alkyl and C1-C4hydroxyalkyl groups; m is 1 or 2; and the remaining substituent(s) R15, R16 and R17 are, independently, amino, C1-C12alkyl, C1-C12alkoxy, C1-C12alkylthio, mono- or di-C1-C12alkylamino, phenyl, phenylthio, anilino or N-phenyl-Nxe2x80x94C1-C4alkylamino, preferably N-phenyl-N-methylamino or N-phenyl-N-ethylamino, the respective phenyl substituents being optionally substituted by C1-C12alkyl or -alkoxy, C5-C8cycloalkyl or halogen.
A third preferred class of triazine UV absorbers is that having the formula: 
in which R18 is hydrogen or hydroxy; R19 and R20, independently, are hydrogen or C1-C4alkyl; n1 is 1 or 2; and B is a group of formula: 
in which n has its previous significance and is preferably 2 or 3; Y1 and Y2, independently, are C1-C4alkyl optionally substituted by halogen, cyano, hydroxy or C1-C4alkoxy or Y1 and Y2, together with the nitrogen atom to which they are each attached, form a 5-7 membered heterocyclic ring, preferably a morpholine, pyrrolidine, piperidine or hexamethyleneimine ring; Y3 is hydrogen, C3-C4alkenyl or C1-C4alkyl optionally substituted by cyano, hydroxy or C1-C4alkoxy or Y1, Y2 and Y3, together with the nitrogen atom to which they are each attached, form a pyridine or picoline ring, and X1, is a colourless anion, preferably CH3OSO3xe2x8ax96 or C2H5OSO3xe2x8ax96.
One preferred class of triazole WV absorbers is that having the formula: 
in which
T1 is chlorine or, preferably, hydrogen; and
T2 is a C8-C30, preferably C8-C16, especially C9-C12alkyl group. T2 may be a random statistical mixture of at least three isomeric branched sec. C8-C30, preferably C8-C16, especially C9-C12alkyl groups, each having the formula xe2x80x94CH(E1)E2 in which E1 is a straight chain C1-C4alkyl group and E2 is a straight chain C4-C15alkyl group, the total number of carton atoms in E1 and E2 being from 7 to 29.
A second preferred class of triazole UV absorbers is that having the formula: 
in which M has its previous significance, but is preferably sodium, and T3 is hydrogen, C1-C12alkyl or benzyl.
A third preferred class of triazole UV absorbers is that having the formula: 
in which B has its previous significance.
In the compounds of formulae (4) to (9), C1-C12Alkyl groups R15, R16, R17 and T3 may be methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert.-butyl,n-amyl, n-hexyl, n-heptyl, n-octyl, isooctyl, n-nonyl, n-decyl, n-undecyl and n-dodecyl, methyl and ethyl being preferred, except in the case of T3 for which isobutyl is preferred. C8-C30alkyl groups T2 include sec.octyl, decyl, dodecyl, tridecyl, tetradecyl, hexadecyl, octadecyl, eicosyl and triacontyl groups.
C1-C5Alkoxy groups R13 or R14 may be, e.g., methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert.-butoxy or n-amyloxy, preferably methoxy or ethoxy, especially methoxy. C1-C12Alkoxy groups R15, R16 and R17 include those indicated for the C1-C5alkoxy groups R13 or R14 together with, e.g., n-hexoxy, n-heptoxy, n-octoxy, isooctoxy, n-nonoxy, n-decoxy, n-undecoxy and n-dodecoxy, methoxy and ethoxy being preferred.
C1-C12Alkylthio groups R15, R16 and R17 may be, e.g., methylthio, ethylthio, n-propylthio, isopropylthio, n-butylthio, isobutylthio, tert.-butylthio, n-amylthio, hexylthio, n-heptylthio, n-octylthio, isooctylthio, n-nonylthio, n-decylthio, n-undecylthio and n-dodecylthio, methylthio and ethylthio being preferred.
C1-C12Mono- or di-alkylamino groups R15, R16 and R17 include, e.g., mono- or di-methylamino, ethylamino, n-propylamino, isopropylamino, n-butylamino, isobutylamino, tert.-butylamino, n-amylamino, n-hexylamino, n-heptylamino, n-octylamino, isooctylamino, n-nonylamino, n-decylamino, n-undecylamino and n-dodecylamino, mono- or di-methylamino or ethylamino being preferred.
The alkyl radicals in the mono-, di-, tri- or tetra-C1-C4alkylammonium groups M are preferably methyl. Mono-, di- or tri-C1-C4hydroxyalkylammonium groups M are preferably those derived from ethanolamine, di-ethanolamine or tri-ethanolamine. When M is ammonium that is di- or tri-substituted by a mixture of C1-C4alkyl and C1-C4hydroxyalkyl groups, it is preferably N-methyl-N-ethanolamine or N,N-dimethyl-N-ethanolamine. M is preferably, however, hydrogen or sodium.
Preferred compounds of formula (4) are those having the formulae: 
The compounds of formula (4) are known and may be prepared e.g. by the method described in U.S. Pat. No. 3,118,887.
Preferred compounds of formula (5) are those having the formula: 
in which R21 and R22, independently, are C1-C12alkyl, preferably methyl; m is 1 or 2; M1 is hydrogen, sodium, potassium, calcium, magnesium, ammonium or tetra-C1-C12alkylammonium, preferably hydrogen; and n2 and n3, independently, are 0, 1 or 2, preferably 1 or 2.
Particularly preferred compounds of formula (18) are:
2,4-diphenyl-6-[2-hydroxy-4-(2-hydroxy-3-sulfopropoxy)-phenyl]-1,3,5-triazine;
2-phenyl-4,6-bis-[2-hydroxy-4-(2-hydroxy-3-sulfopropoxy)- phenyl]-1,3,5-triazine;
2,4-bis(2,4-dimethylphenyl)-6-[2-hydroxy-4-(2-hydroxy-3-sulfopropoxy)-phenyl]-1,3,5-triazine; and
2,4-bis(4methylphenyl)-6-[2-hydroxy-4-(2-hydroxy-3-sulfopropoxy)-phenyl]-1,3,5-triazine.
The compounds of formula (5) are known and may be prepared in the manner, e.g., described in U.S. Pat. No. 5,197,991.
The compounds of formula (8) are known and may be prepared in the manner, e.g., described in U.S. Pat. No. 4,675,352.
The compounds of formula (9) are known and may be prepared in the manner, e.g., described in EP-A-0 314 620.
The compounds of formula (10) are known and may be prepared in the manner, e.g., described in EP-A-0 357 545.
Some of the UV absorbers used in the method of the present invention may be only sparingly soluble in water and may need to be applied in dispersed form. For this purpose, they may be milled with an appropriate dispersant, conveniently using quartz balls and an impeller, down to a particle size of 1-2 microns.
As dispersing agents for such sparingly-soluble UV absorbers there may be mentioned: acid esters or their salts of alkylene oxide adducts, e.g., acid esters or their salts of a polyadduct of 4 to 40 moles of ethylene oxide with 1 mole of a phenol, or phosphoric acid esters of the adduct of 6 to 30 moles of ethylene oxide with 1 mole of 4-nonylphenol, 1 mole of dinonylphenol or, especially, with 1 mole of compounds which have been produced by the addition of 1 to 3 moles of styrenes on to 1 mole of phenol;
polystyrene sulphonates;
fatty acid taurides;
alkylated diphenyloxide-mono- or -di-sulphonates;
sulphonates; of polycarboxylic acid esters;
addition products of 1 to 60, preferably 2 to 30 moles of ethylene oxide and/or propylene oxide on to fatty amines, fatty amides, fatty acids or fatty alcohols, each having 8 to 22 carbon atoms, or on to tri- to hexavalent C3-C6alkanols, the addition products having been converted into an acid ester with an organic dicarboxylic acid or with an inorganic polybasic acid;
lignin sulphonates; and, in particular
formaldehyde condensation products, e.g., condensation products of lignin sulphonates and/or phenol and formaldehyde; condensation products of formaldehyde with aromatic sulphonic acids, e.g., condensation products of ditolylethersulphonates and formaldehyde; condensation products of naphthalenesulphonic acid and/or naphthol- or naphthylaminesulphonic acids and formaldehyde; condensation products of phenolsulphonic acids and/or sulphonated dihydroxydiphenylsulphone and phenols or cresols with formaldehyde and/or urea; or condensation products of diphenyloxide-disulphonic acid derivatives with formaldehyde.
In addition to the UV absorber, the composition according to the present invention may also contain a minor proportion of one or more adjuvants. Examples of adjuvants include emulsifiers, perfumes, colouring dyes, opacifiers, fluorescent whitening agents, bactericides, nonionic surfactants, anti-gelling agents such as nitrites or nitrates of alkali metals, especially sodium nitrate, and corrosion inhibitors such as sodium silicate.
The amount of each of these optional adjuvants preferably ranges from 0.05 to 5% by weight of the composition.
A particularly preferred optional adjuvant is a cationic, amphoteric or anionic fluorescent whitening agent.
The cationic fluorescent whitening agent is preferably of the bistyrylphenyl class or phosphinic acid salt class; the amphoteric fluorescent whitening agent is preferably of the styrene or amine, oxide class; and the anionic fluorescent whitening agent is preferably of the aminostilbene, dibenzofuranylbiphenyl or bistyrylphenyl class.
One preferred class of cationic bistyrylphenyl fluorescent whitening agent is that having the formula: 
in which Y is arylene, preferably 1,4-phenylene or 4,4xe2x80x2-phenylene, each optionally substituted by (chloro, methyl or methoxy; q is 1 or 2; R23 is hydrogen, chloro, C1-C4-alkyl, C1-C4-alkoxy, cyano or C1-C4-alkoxycarbonyl; R24 and R25 are C1-C4-alkyl, chloroethyl, methoxyethyl, xcex2-ethoxyethyl, xcex2-acetoxyethyl or xcex2-cyanoethyl, benzyl or phenylethyl; R26 is C1-C4-alkyl, C2-C3-hydroxyalkyl, xcex2-hydroxy-xcex3-chloropropyl, xcex2-cyanoethyl car C1-C4-alkoxy-carbonylethyl; and A is an anion, preferably the chloride, bromide, iodide, methosulfate, ethosulfate, benzenesulfonate or p-toluenesulfonate anion when R26 is C1-C4-alkyl or A is preferably the formate, acetate, propionate or benzoate anion when R26 is xcex2-hydroxy-xcex3-chloropropyl, xcex2-cyanoethyl or C1-C4-alkoxy-carbonylethyl.
Preferred compounds of formula (19) are those in which Y is 1,4phenylene or 4,4-diphenylene; R23 is hydrogen, methyl or cyano; R24 and R25 are each methyl or cyano; and R26 and A have their previously indicated preferred meanings.
One particularly preferred compound of formula (19) is that having the formula: 
The compound; of formula (19) and their production are described in U.S. Pat. No. 4,009,193.
A further prefer red class of cationic bistyrylphenyl fluorescent whitening agent is that having the formula: 
in which R23 and q have their previous significance; Y4 is C2-C4-alkylene or hydroxypropylene; R27 is C1-C4-alkyl or, together with R28 and the nitrogen to which they are each attached, R27 forms a pyrrolidine, piperidine, hexamethyleneimine or morpholine ring; R28 is C1-C4-alkyl or, together with R27 and the nitrogen to which they are each attached, R28 forms a pyrrolidine, piperidine, hexamethyleneimine or morpholine ring; R29 is hydrogen, C1-C4-alkyl, C3-C4-alkenyl, C1-C4-akoxycarbonylmethyl, benzyl, C2-C4-hydroxyalkyl, C2-C4-cyanoalkyl or, together with R27 and R28 and the nitrogen atom to which they are each attached, R29 forms a pyrrolidine, piperidine, hexamethyleneimine or morpholine ring; A has its previous significance; and p is 0 or 1.
Preferred compounds of formula (21) are those in which q is 1; R23 is hydrogen, chlorine, C1-C4-alkyl or C1-C4-alkoxy; Y4 is (CH2)2; R27 and R28 are the same and each is methyl or ethyl; R29 is methyl or ethyl; p is 1; and A is CH3OSO3 or C2H5OSO3.
The compounds of formula (21) and their production are described in U.S. Pat. No. 4,339,393.
A further preferred class of cationic bistyrylphenyl fluorescent whitening agent is that having the formula: 
in which R23, Y4, A, p and q have their previous significance; R30 and R31, independently, are C1-C4-alkyl or C2-C3-alkenyl or R30 and R31, together with the nitrogen atom to which they are attached, form a pyrrolidine, piperidine, hexamethyleneimine or morpholine ring; R32 is hydrogen, C1-C4-alkyl or C2-C3-alkenyl or R30, R31 and R32, together with the nitrogen atom to which they are attached, form a pyridine or picoline ring; and Z is sulfur, xe2x80x94SO2xe2x80x94, xe2x80x94SO2NHxe2x80x94, xe2x80x94Oxe2x80x94C1-C4-alkylene-COOxe2x80x94 or xe2x80x94OCOxe2x80x94.
Preferred compounds of formula (22) are those in which R23 is hydrogen, chlorine, C1-C4-alkyl or C1-C4-alkoxy; R30 and R31, independently, are C1-C4-alkyl or, together with the nitrogen atom to which they are attached, form a pyrrolidine, piperidine or morpholine ring; R32 is hydrogen, C1-C4-alkyl or C3-C4-alkenyl or R30, R31 and R32, together with the nitrogen atom to which they are attached, form a pyridine ring; and Z is sulfur, xe2x80x94SO2xe2x80x94 or xe2x80x94SO2NHxe2x80x94,.
The compounds of formula (22) and their production are described in U.S. Pat. No. 4,486,352.
A further preferred class of cationic bistyrylphenyl fluorescent whitening agent is that having the formula: 
in which R23, R30, R31, R32, Y4, A, p and q have their previous significance.
Preferred compounds of formula (23) are those in which q is 1; R23 is hydrogen, chlorine, C1-C4-alkyl or C1-C4-alkoxy; R30 and R31, independently, are C1-C4-alkyl or, together with the nitrogen atom to which they are attached, form a pyrrolidine, piperidine or morpholine ring; R32 is hydrogen, C1-C4-alkyl or C3-C4-alkenyl or R30, R31 and R32, together with the nitrogen atom to which they are attached, form a pyridine ring.
The compounds of formula (23) and their production are described in U.S. Pat. No. 4,602,087.
One preferred class of amphoteric styrene fluorescent whitening agent is that having the formula: 
in which R23, R30, R31, Y4 and q have their previous significance and Z1 is oxygen, sulfur, a direct bond, xe2x80x94COOxe2x80x94, xe2x80x94CON(R32)xe2x80x94 or xe2x80x94SO2N(R32)xe2x80x94 in which R32 is hydrogen, C1-C4-alkyl or cyanoethyl; and Q is xe2x80x94COOxe2x80x94 or xe2x80x94SO3.
Preferred compounds of formula (24) are those in which Z1 is oxygen, a direct bond, xe2x80x94CONHxe2x80x94, xe2x80x94SO2NHxe2x80x94 or xe2x80x94COOxe2x80x94, especially oxygen; q is 1; R30 is hydrogen, C1-C4-alkyl, methoxy or chlorine; and R31, R32, Y4 and Q have their previous significance.
The compounds of formula (24) and their production are described in U.S. Pat. No. 4,478,598.
One preferred class of amine oxide fluorescent whitening agent is that having the formula: 
in which q has its previous significance; W is a whitener radical selected from a 4,4xe2x80x2-distyrylbiphenyl, 4,4xe2x80x2-divinyl-stilbene, and a 1,4xe2x80x2-distyrylbenzene, each optionally substituted by one to four substituents selected from halogen, C1-C4alkyl, C1-C4-hydroxyalkyl, C1-C4-halogenoalkyl, C1-C4-cyanoalkyl, C1-C4-alkoxy-C1-C4-alkyl, phenyl-C1-C4-alkyl, carboxy-C1-C4-alkyl, carb-C1-C4-alkoxy-C1-C4-alkyl, C1-C4-alkenyl, C5-C8-cycloalkyl, C1-C4-alkoxy, C1-C4alkenoxy, C1-C4-alkoxycarbonyl, carbamoyl, cyano, C1-C4-alkyl-sulfonyl, phenylsulfonyl, C1-C4-alkoxysulfonyl, sulfamoyl, hydroxyl, carboxyl, sulfo and trifluoromethyl, Z2 is a direct bond between B and Y5, an oxygen atom, a sulfur atom, xe2x80x94SO2xe2x80x94, xe2x80x94SO2xe2x80x94Oxe2x80x94, xe2x80x94COOxe2x80x94, xe2x80x94CON(35)xe2x80x94 or xe2x80x94SO2N(R35)xe2x80x94 in which R35 is hydrogen or C1-C4-alkyl optionally substituted by halogen, cyano, hydroxyl, C2-C5-carbalkoxy, C1-C4-alkoxy, phenyl, chlorophenyl, methylphenyl, methoxyphenyl, carbamoyl or sulfamoyl; Y5 is C2-C4-alkylene or C2-C4-alkyleneoxy-C2-C4-alkylene, each optionally substituted by halogen, hydroxyl, C2-C4-carbalkoxy, C1-C4-alkoxy, phenyl, chlorophenyl, methylphenyl, methoxyphenyl, carbamoyl or sulfamoyl; and R33 and R34, independently, are C5-C8-cycloalkyl, C1-C4-alkyl or phenyl, each optionally substituted by halogen, hydroxyl, C2-C5-carbalkoxy, C1-C4-alkoxy, phenyl, chlorophenyl, methylphenyl, methoxyphenyl, carbamoyl or sulfamoyl; in which, in all the carbamoyl or sulfamoyl groups, the nitrogen atom is optionally substituted by one or two C1-C4-alkyl, C1-C4-hydroxyalkyl, C2-C5-cyanoalkyl, C1-C4-halogenoalkyl, benzyl or phenyl groups.
Preferred whitener radicals W are those having the formula: 
in which q has its previous significance and the rings are optionally substituted as indicated above.
Preferably Z2 is oxygen, xe2x80x94SO2xe2x80x94 or xe2x80x94SO2N(R36)xe2x80x94 in which R36 is hydrogen or C1-C4-alkyl optionally substituted by hydroxyl, halogen or cyano; and R33 and R34, independently, are C1-C4-alkyl optionally substituted by halogen, cyano, hydroxyl, C1-C4-alkoxy, phenyl, chlorophenyl, methylphenyl, methoxyphenyl or C1-C5-alkoxycarbonyl. Other preferred compounds of formula (25) are those in which Z2 is oxygen, sulfur, xe2x80x94SO2xe2x80x94, xe2x80x94CON(R36)xe2x80x94 or xe2x80x94SO2N(R36)xe2x80x94 in which R36 is hydrogen or C1-C4-alkyl optionally substituted by hydroxyl, halogen or cyano; and Y5 is C1-C4-alkylene.
The compounds of formula (25) and their production are described in U.S. Pat. No. 4,539,161.
One preferred class of cationic phosphinic acid salt fluorescent whitening agent is that having the formula: 
in which q has its previous significance; W1 is whitener radical; Z3 is a direct bond, xe2x80x94SO2xe2x80x94C1-C4-alkyleneoxy, xe2x80x94SO2xe2x80x94C2-C4-alkylene-COOxe2x80x94, xe2x80x94SO2xe2x80x94, xe2x80x94COOxe2x80x94, xe2x80x94SO2xe2x80x94C2-C4-alkylene-CON(R42)xe2x80x94 or xe2x80x94SO2N(R42)xe2x80x94 in which R42 is hydrogen or C1-C4-alkyl, optionally substituted by hydroxyl, halogen or cyano; R37 is C1-C4-alkyl or C2-C4-alkenyl, each optionally substituted by halogen, cyano, hyxdroxy, C1-C4-alkoxycarbonyl or C1-C4-alkoxycarbonyloxy, or R37 is benzyl, optionally substituted by halogen, C1-C4-alkyl or C1-C4-alkoxy, or R37, together with R38 or Z3, forms a pyrrolidine, piperidine or morpholine radical; R38 is C1-C4-alkyl or C2-C4-alkenyl, each optionally substituted by halogen, cyano, hydroxy, C1-C4-alkoxycarbonyl or C1-C4-alkylcarbonyloxy, or R38 is benzyl, optionally substituted by halogen, C1-C4-alkyl or C1-C4-alkoxy, or R38, together with R37, forms a pyrrolidine, piperidine or morpholine radical; R39 is C1-C4-alkyl; R40 is hydrogen or C1-C4-alkyl, optionally substituted by cyano, hydroxy, C1-C4-alkoxycarbonyl or C1-C4-alkylcarbonyloxy; and R41 is C1-C4-alkyl.
Preferably, whitener radical W1 has the formula: 
each optionally substituted by one to four substituents selected from halogen, C1-C4-alkyl, C1-C4-hydroxyalkyl, C1-C4-halogenoalkyl, C1-C4-cyanoalkyl, C1-C4-alkoxy-C1-C4-alkyl, phenyl-C1-C4-alkyl, carboxy-C1-C4-alkyl carb-C1-C4alkoxy-C1-C4-alkyl, C1-C4alkenyl, C5-C8-cycloalkyl, C1-C4-alkoxy, C1-C4-alkenoxy, C1-C4-alkoxycarbonyl, carbamoyl, cyano, C1-C4-alkyl-sulfonyl, phenylsulfonyl, C1-C4-alkoxysulfonyl, sulfamoyl, hydroxyl, carboxyl, sulfo and trifluoromethyl.
The compounds of formula (26) and their production are described in GB-A2 023 605.
Preferred bis(triazinyl)diaminostilbene anionic fluorescent whitening agents for use in the present invention are those having the formula: 
Preferred dibenzofuranylbiphenyl anionic fluorescent whitening agents for use in the present invention are those having the formula: 
Preferred anionic bistyrylphenyl fluorescent whitening agents for use in the present invention are those having the formula: 
In the formulae (27) to (29), R42 is phenyl optionally substituted by one or two SO3M groups and R43 is NHxe2x80x94C1-C4-alkyl, N(C1-C4-alkyl)2, NHxe2x80x94C1-C4-alkoxy, N(C1-C4-alkoxy)2, N(C1-C4-alkyl)(C1-C4-hydroxyalkyl), N(C1-C4-hydroxyalkyl)2; R44 is H, C1-C4-alkyl, CN, Cl or SO3M; R45 and R46, independently, are H, C1-C4-alkyl, SO3M, CN, Cl or Oxe2x80x94C1-C4-alkyl, provided that at least two of R44, R45 and R46 are SO3M and the third group has solubilising character, R47 is H, SO3M, Oxe2x80x94C1-C4-alkyl, CN, Cl, COOxe2x80x94C1-C4-alkyl, or CON(C1-C4-alkyl)2; M is is H, Na, K, Ca, Mg, ammonium, mono-, di-, tri- or tetra-C1-C4-alkylammonium, mono-, di- or tri-C1-C4-hydroxyalkylammonium or ammonium that is di- or tri-substituted with by a mixture of C1-C4-alkyl and C1--C4-hydroxyalkyl groups; and r is 0 or 1.
In the compounds of formulae (27) to (29), C1-C4-alkyl groups are, e.g., methyl, ethyl, n-propyl, isopropyl and n-butyl, especially methyl. Aryl groups are naphthyl or, especially, phenyl.
Specific examples of preferred compounds of formula (27) are those having the formulae: 
Preferred examples of compounds of formula (28) are those of formulae: 
Preferred examples of compounds of formula (29) are those having the formulae: 
The compounds of formulae (27) to (29) are known and may be obtained by known methods.
The present invention also provides, as a third apect, a method for the treatment of a textile article, in particular to improve its SPF, comprising applying, to a previously washed article, a fabric rinse composition comprising:
a) 0.1 to 20, preferably 1 to 10% by weight of a UV absorber selected from a hydroxyaryl-1,3,5-triazine, a sulphonated-1,3,5-triazine, an o-hydroxyphenylbenzotriazole or a 2-aryl-2H-benzotriazole, based on the total weight of the composition;
b) a fabric care ingredient; and
c) the remainder being substantially water.
Preferably, the fabric care ingredient is a fabric softener, a stain release or stain repellant ingredient or a water-proofing agent, which is preferably present in an amount of from 5 to 25%, especially from 10 to 20% by weight, based on the total weight of the composition.
A preferred method for the treatment of a textile article, in particular to improve its SPF, comprises applying, to the previously washed article, a rinse cycle fabric softener composition comprising:
a) 0.05 to 5, preferably 0.1 to 1.5% by weight of a UV absorber selected from a hydroxyaryl-1,3,5-triazine, a sulphonated-1,3,5-triazine, an o-hydroxyphenylbenzotriazole or a 2-aryl-2H-benzotriazole, based on the total weight of the composition;
b) 5 to 25preferably 10 to 20% by weight of a cationic fabric softening agent, based on the total weight of the composition; and
c) the remainder being substantially water.
The textile article treated according to the method of the present invention may be composed of any of a wide range of types of fibre such as wool, polyamide, cotton, polyester, polyacrylic, silk or any mixture thereof.
The method and composition of the present invention, in addition to providing protection to the skin, also increase the useful life of a textile article treated according to the present invention, for example by preserving its tear strength and/or its lightfastness.
The following Examples further illustrate the present invention.